CN115197147B - Perovskite single crystal material based on imidazole organic cations, preparation method and application thereof - Google Patents
Perovskite single crystal material based on imidazole organic cations, preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 127
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 102
- -1 imidazole organic cations Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000012296 anti-solvent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004020 luminiscence type Methods 0.000 claims description 13
- 230000007547 defect Effects 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000000498 ball milling Methods 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 238000001144 powder X-ray diffraction data Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 241000341910 Vesta Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention relates to a perovskite single crystal material based on imidazole organic cations, a preparation method and application thereof, and belongs to the technical field of organic-inorganic hybrid materials. The chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 Or (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 ，(C 3 H 5 N 2 ) + Is imidazole organic cation. The imidazole and PbO are added into the halogen acid solution according to the molar ratio of 4:1-16:1, and the halogen acid solution is prepared by adopting an antisolvent method or a program cooling method. The single crystal material has excellent structural stability and thermal stability. The single crystal material can realize white fluorescent emission of a single component.
Description
Technical Field
The invention relates to a perovskite single crystal material based on imidazole organic cations, a preparation method and application thereof, and belongs to the technical field of organic-inorganic hybrid materials.
Background
The single-component white light emitting material can greatly simplify the structure of the solid-state lighting equipment, and can avoid the phenomena of unstable luminescence and the like caused by different self-absorption effects and decomposition speeds due to the mixed fluorescent material. Compared with the traditional inorganic or organic fluorescent powder, the low-dimensional organic-inorganic hybridization perovskite is simple to prepare and low in cost, and is a single-component white fluorescent emission material with excellent performance. Among low-dimensional perovskite materials, current research on two-dimensional perovskite is mature, and one-dimensional and zero-dimensional perovskite is less studied. While the most common in one dimension are face sharing and edge sharing, one-dimensional point sharing connected perovskites have not been reported. Meanwhile, most of perovskite white light material luminescence is derived from self-trapping exciton luminescence, and reports about intrinsic defect luminescence are few.
Disclosure of Invention
In view of the above, the invention aims to provide a perovskite single crystal material based on imidazole organic cations, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
perovskite single crystal material based on imidazole organic cations, wherein the single crystal material has a chemical formula (C) 3 H 5 N 2 ) 3 PbBr 5 Or (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 ，(C 3 H 5 N 2 ) + Is an imidazole organic cation, (C) 3 H 5 N 2 ) 3 PbBr 5 The lead bromine octahedron is in a one-dimensional point sharing structure, is connected into a single-chain structure through a point sharing mode, extends along the a-axis direction, and surrounds the chain structure by imidazole organic cations; (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 Pb atoms and Cl atoms coordinate to form decahedrons and octahedrons respectively, the lead-chlorine decahedrons and the lead-chlorine octahedrons are connected in a shared mode of points, edges and faces to form a pore structure, and imidazole organic cations are periodically distributed in the pore structure.
Preferably, the (C 3 H 5 N 2 ) 3 PbBr 5 The unit cell parameters of (2) are: α＝66.96°、β＝86.89°、γ＝88.63°。
preferably, the (C 3 H 5 N 2 ) 4 Pb 6 Cl 16 The unit cell parameters of (2) are: α＝90°、β＝98.937°、γ＝90°。
the invention discloses a preparation method of perovskite single crystal material based on imidazole organic cations, which comprises the following steps:
imidazole and PbO are added into a halogen acid solution according to the molar ratio of 4:1-16:1, and an anti-solvent method or a program cooling method is adopted to prepare a perovskite single crystal material; wherein the halogen acid is HBr or HCl.
Preferably, when the anti-solvent method is adopted for preparation, the anti-solvent is diethyl ether.
Preferably, when the preparation is carried out by adopting a programmed cooling method, the heating temperature is 90-110 ℃, and the heat preservation is carried out for 1.5-2.5 hours.
Preferably, when the program is cooled, the cooling rate is 1-2 ℃/h.
Preferably, the molar ratio of imidazole to PbO is 8:1-12:1.
The invention discloses application of perovskite single crystal material based on imidazole organic cations, which is used as a white fluorescent luminescent material.
Preferably, the (C 3 H 5 N 2 ) 3 PbBr 5 Is an intrinsic defect state luminescence.
Advantageous effects
The invention provides a perovskite single crystal material based on imidazole organic cations, which takes imidazole cations as organic cations, wherein (C) 3 H 5 N 2 ) 3 PbBr 5 Is a typical 1D point sharing structure, lead bromine octahedrons are connected into a single-chain structure through a point sharing form, and extend along the a-axis direction, and imidazole cations are surrounded by the chain structure. (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 Pb atoms and Cl atoms in the unit cells form decahedron and octahedron, lead-chlorine polyhedrons are connected in a shared mode through points, edges and faces, a complex 'hole' structure is formed, and imidazole cations are periodically distributed in the 'hole' structure. The single crystal material has excellent structural stability and thermal stability.
The invention provides a preparation method of perovskite monocrystal material based on imidazole organic cations, which is characterized in that the near-perfect monocrystal material with larger size, transparent crystal, no obvious crystal boundary, fewer crystal defect states and ordered structure rule long range is obtained by strictly controlling the dosage of imidazole and PbO and adopting an antisolvent method or a program cooling method.
The invention provides an application of perovskite single crystal material based on imidazole organic cations, wherein the single crystal material can realize white fluorescence emission of a single component; and (C) 3 H 5 N 2 ) 3 PbBr 5 Is an intrinsic defect state luminescence.
Drawings
FIG. 1 is a single crystal diffraction structure of a single crystal material according to example 1.
FIG. 2 is a powder X-ray diffraction (PXRD) pattern of the single crystal material of example 1.
FIG. 3 is an ultraviolet visible absorption spectrum (Abs) and a fluorescence emission spectrum (PL) of the single crystal material described in example 1.
Fig. 4 is a 3D photoluminescence scan spectrum of the single crystalline material described in example 1.
FIG. 5 is a fluorescence emission spectrum of the single crystal material of example 1 after ball milling.
FIG. 6 is a fluorescence emission spectrum of the single crystal material of example 1 after ultrasonic acetone recrystallization.
FIG. 7 is a PXRD pattern of the single crystal material of example 1 after ultrasonic acetone recrystallization.
Fig. 8 is a time resolved photoluminescence spectrum (TRPL) plot of the single crystalline material described in example 1.
FIG. 9 is a Thermogravimetric (TG) plot of mass versus temperature for a single crystal material of example 1.
FIG. 10 shows the morphology of the single crystal material of example 1 (left) and the luminescence photograph under UV lamp irradiation (right).
Fig. 11 is a photograph of a WLED lamp coated with the single crystal material of example 1 in the off (left) and on (right) states.
FIG. 12 is a single crystal diffraction pattern diagram of a single crystal material as described in example 6.
FIG. 13 is a powder X-ray diffraction pattern of a single crystal material as described in example 6.
FIG. 14 is an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the single crystal material of example 6.
Fig. 15 is a time resolved photoluminescence spectrum of the single crystalline material described in example 6.
FIG. 16 is a thermogravimetric plot of mass versus temperature for the single crystal material of example 6.
FIG. 17 is a photograph of the morphology (left) and luminescence (right) of the single crystal material of example 6 under irradiation of an ultraviolet lamp.
FIG. 18 is a comparison of powder X-ray diffraction patterns of the material described in comparative example 1 with simulated XRD patterns of the single crystal material described in example 1.
FIG. 19 is a single crystal diffraction structure of the single crystal material of comparative example 2.
FIG. 20 is a powder X-ray diffraction pattern of the single crystal material of comparative example 2.
FIG. 21 is a photograph of a single crystal material of comparative example 2 under irradiation of an ultraviolet lamp.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the following examples:
(1) Single crystal diffraction test: k using Mo with an Xta LAB PRO 007HF single crystal X-ray diffractometer α And (3) ray detection, and deriving an analog XRD pattern through VESTA.
(2) PXRD test: the diffraction was scanned using a D8 ADVANCE X-ray diffractometer using a copper X-ray tube (standard) radiation at 40kV and 40mA current at room temperature in 5 DEG/min steps over the range of 5-60 deg.
(3) Ultraviolet visible absorption spectrum: a UV-3600 ultraviolet-visible-near infrared spectrophotometer was used.
(4) Photo-induced fluorescence emission spectrum: FLS980 fluorescence spectrometer (Edinburgh instruments Co.) was used.
(5) 3D photoluminescence scanning spectrum: measured using a Horiba JY Fluoromax-4 fluorometer.
(6) Time resolved photoluminescence spectra: FLS980 fluorescence spectrometer (Edinburgh instruments Co.) was used.
(7) Thermogravimetric analysis: a STA449F5 thermogravimetric analyzer was used.
Example 1
A method for preparing a one-dimensional point sharing perovskite single crystal material by adopting an anti-solvent method comprises the following steps:
solid PbO (0.225 mmol,50 mg) and imidazole (1.8 mmol,122 mg) were mixed with 2mL of 48% hydrobromic acid in mass fraction in a 5mL glass bottle at room temperature (25 ℃), placed into a large centrifuge tube containing ethyl ether, the ethyl ether level was below the glass bottle mouth, the glass bottle was open, and the large centrifuge tube was left to stand after sealing. And (3) cleaning the crystal from the mother liquor by using acetone after three days to obtain the one-dimensional point sharing perovskite single crystal material.
The single crystal material was subjected to single crystal diffraction test, the single crystal structure of the material is shown in FIG. 1, and the result shows that the chemical formula of the material is (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure of the material is a one-dimensional point sharing configuration structure.
The unit cell parameters of the single crystal material are shown in table 1.
Table 1 (C) 3 H 5 N 2 ) 3 PbBr 5 Single crystal structural parameter (296K)
The PXRD results of the single crystal material after ball milling are shown in figure 2, and the PXRD patterns are consistent with the XRD patterns of single crystal simulation, thus further proving (C) 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The results of the ultraviolet visible absorption spectrum (Abs) and the fluorescence emission spectrum (PL) of the single crystal material are shown in fig. 3, and the band gap of the material is 3.40eV calculated according to the absorption spectrum, and the material shows a broad peak emission from an intrinsic defect state at 530nm according to the PL spectrum.
The single crystal materialThe 3D photoluminescence scan spectrum results are shown in fig. 4, and the crystal still shows broadband emission at 530nm when excited by light less than the band gap energy at room temperature (25 ℃). Self-trapping excitons are transient excitons which are generated when excited by light, and therefore when the excitation light energy is less than the band gap, the material does not exhibit self-trapping luminescence. While when excited by light smaller than the band gap energy, the material can exhibit intrinsic defect state luminescence (as shown in the 3D photoluminescence scanning spectrum of FIG. 4), so that it can be reasonably presumed (C 3 H 5 N 2 ) 3 PbBr 5 The broadband white light emission of (2) is mainly due to intrinsic defects of the crystal.
The fluorescence emission spectrum of the single crystal material after ball milling is shown in FIG. 5, which shows that the luminous intensity of the single crystal material after ball milling is greatly reduced, thus (C) 3 H 5 N 2 ) 3 PbBr 5 Is derived from surface defects of the crystal.
The results of fluorescence emission spectra of the single crystal material after acetone ultrasonic and recrystallization are shown in figure 6, which shows that the defects are reduced and eliminated, the (C) 3 H 5 N 2 ) 3 PbBr 5 From the light emission intensity of (C) 3 H 5 N 2 ) 3 PbBr 5 The luminescence of (2) is mainly derived from intrinsic defects of the crystal.
The PXRD results of the single crystal material after acetone ultrasonic and recrystallization are shown in figure 7, and the PXRD graph spectrum is consistent with that of the single crystal before the treatment, thus the acetone ultrasonic and recrystallization treatment is not changed (C) 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The TRPL results for the single crystal material are shown in fig. 8, which shows that the fluorescence decay time of the material at 530nm is 2ns.
The TG curve of the single crystal material is shown in fig. 9, and the result shows that the material has good thermal stability and does not decompose below 230 ℃.
The morphology of the single crystal material is shown in fig. 10 (left), and the result shows that the single crystal material is transparent needle-shaped.
The single crystal material emits white light after being irradiated with 365nm ultraviolet lamp at room temperature (25 ℃) as shown in fig. 10 (right).
Mixing the ground single crystal material powder with AB glue (A is epoxy resin, B is hardener, the mass ratio of A to B is 1:4), uniformly stirring, then coating on a purple light LED, and placing in an oven to cure for 40min at a constant temperature of 80 ℃ to obtain the WLED lamp with white light emission. Photographs of the WLED lamp in the off (left) and on (right) states are shown in fig. 11.
Example 2
In this example, the amount of PbO was 0.225mmol, the amount of imidazole was 0.9mmol, and the remainder was the same as in example 1.
The single crystal diffraction result shows that the chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure is a one-dimensional point sharing configuration structure.
The PXRD pattern of the single crystal material after ball milling is consistent with the XRD pattern of single crystal simulation, and further proves (C 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The single crystal material in this example was slightly smaller in size than the single crystal material described in example 1.
Example 3
In this example, the amount of PbO was 0.225mmol, the amount of imidazole was 3.6mmol, and the remainder was the same as in example 1.
The single crystal diffraction result shows that the chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure is a one-dimensional point sharing configuration structure.
The PXRD pattern of the single crystal material after ball milling is consistent with the XRD pattern of single crystal simulation, and further proves (C 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The single crystal material in this example was slightly smaller in size than the single crystal material described in example 1.
Example 4
A method for preparing a one-dimensional point sharing perovskite single crystal material by adopting a program cooling method comprises the following steps:
solid PbO (0.225 mmol,50 mg) and imidazole (1.8 mmol,122 mg) were mixed with 1mL of 48% by mass hydrobromic acid in a glass tube at room temperature (25 ℃) and heated to 100℃and kept at 2. 2 h, then cooled slowly to room temperature at a rate of 1℃per hour, and the crystals were washed from the mother liquor with acetone to obtain a one-dimensional shared perovskite single crystal material.
The single crystal diffraction result shows that the chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure is a one-dimensional point sharing configuration structure.
The PXRD pattern of the single crystal material after ball milling is consistent with the XRD pattern of single crystal simulation, and further proves (C 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The dimensions of the single crystal material described in this example are similar to those of the single crystal material described in example 1.
Example 5
In this example, the amount of PbO was 0.225mmol, the amount of imidazole was 0.9mmol, and the remainder was the same as in example 4.
The single crystal diffraction result shows that the chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure is a one-dimensional point sharing configuration structure.
The PXRD pattern of the single crystal material after ball milling is consistent with the XRD pattern of single crystal simulation, and further proves (C 3 H 5 N 2 ) 3 PbBr 5 Is a structure of (a).
The single crystal material in this example was slightly smaller in size than the single crystal material described in example 1.
Example 6
A method for preparing perovskite single crystal material by adopting an antisolvent method, which comprises the following steps:
solid PbO (0.225 mmol,50 mg) and imidazole (1.8 mmol,122 mg) were mixed with 2mL of 48% hydrochloric acid in mass fraction in a 5mL glass bottle at room temperature (25 ℃), placed into a large centrifuge tube containing ethyl ether, the ethyl ether level was below the glass bottle mouth, the glass bottle was open, and the large centrifuge tube was left to stand after sealing. After three days, the crystals were washed from the mother liquor with acetone to obtain a perovskite single crystal material.
The single crystal material was subjected to single crystal diffraction test, the single crystal structure of the material is shown in FIG. 12, and the result shows that the chemical formula of the material is (C 3 H 5 N 2 ) 4 Pb 6 Cl 16 The unit cell contains 6 Pb atoms in different chemical environments, the Pb atoms coordinate with Cl atoms to form decahedron and octahedron, the Pb-Cl polyhedrons are connected in a shared mode through points, edges and faces to form a complex 'hole' -shaped structure, and imidazole cations are periodically distributed in the 'hole' -shaped structure.
The unit cell parameters of the single crystal material are shown in table 2.
Table 2 (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 Single crystal structural parameter (296K)
The PXRD results of the single crystal material after ball milling are shown in FIG. 13, and the PXRD patterns are consistent with the XRD patterns of single crystal simulation, thus further confirming (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 Is a structure of (a).
The results of ultraviolet visible absorption spectrum (Abs) and fluorescence emission spectrum (PL) of the single crystal material are shown in fig. 14, and the band gap of the material is 3.45eV calculated according to the absorption spectrum, and the material shows broad peak emission at 550nm according to the PL spectrum.
The TRPL results of the single crystal material are shown in fig. 15, which shows that the fluorescence decay time of the material at 550nm is 5.7ns.
The TG curve of the single crystal material is shown in fig. 16, and the result shows that the material has relatively poor thermal stability and does not decompose below 130 ℃.
The morphology of the single crystal material is shown in fig. 17 (left), and the result shows that the single crystal material is transparent needle-shaped.
The single crystal material emits white light after irradiation with 365nm ultraviolet lamp at room temperature (25 ℃) as shown in fig. 17 (right).
Comparative example 1
In this comparative example, the amount of PbO was 0.225mmol, the amount of imidazole was 0.45mmol, and the remainder was the same as in example 1.
The powder X-ray diffraction results of the material indicated that the crystal structure of the material was changed as shown in FIG. 18, which illustrates that the material of this comparative example was different from that of the material of example 1 (C 3 H 5 N 2 ) 3 PbBr 5 The crystal structure is different.
Comparative example 2
In this comparative example, the amount of PbO used was 0.225mmol, the amount of imidazole used was 0.225mmol, and the haloacid was hydroiodic acid, in the remainder of example 1.
The single crystal material was subjected to single crystal diffraction test, the single crystal structure of the material is shown in FIG. 19, and the result shows that the material has the chemical formula (C 3 H 5 N 2 ) 3 Pb 3 I 9 。
The PXRD results of the single crystal material after ball milling are shown in FIG. 20, and the PXRD patterns are consistent with the XRD patterns of single crystal simulation, and further prove that (C) 3 H 5 N 2 ) 3 Pb 3 I 9 Is a structure of (a).
As shown in FIG. 21, the luminescence phenomenon cannot be observed by the naked eye after the single crystal material is irradiated by a 365nm ultraviolet lamp at room temperature (25 ℃).
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalents or modifications that fall within the spirit and principles of the invention.
Claims (8)
1. A perovskite single crystal material based on imidazole organic cations, which is characterized in that: by a means ofThe chemical formula of the single crystal material is (C 3 H 5 N 2 ) 3 PbBr 5 Or (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 ，(C 3 H 5 N 2 ) + Is an imidazole organic cation, (C) 3 H 5 N 2 ) 3 PbBr 5 The lead bromine octahedron is in a one-dimensional point sharing structure, is connected into a single-chain structure through a point sharing mode, extends along the a-axis direction, and surrounds the chain structure by imidazole organic cations; (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 Pb atoms and Cl atoms coordinate to form decahedrons and octahedrons respectively, the lead-chlorine decahedrons and the lead-chlorine octahedrons are connected in a shared mode of points, edges and faces to form a pore structure, and imidazole organic cations are periodically distributed in the pore structure;
said (C) 3 H 5 N 2 ) 3 PbBr 5 The unit cell parameters of (2) are:α＝66.96°、β＝86.89°、γ＝88.63°；
said (C) 3 H 5 N 2 ) 4 Pb 6 Cl 16 The unit cell parameters of (2) are:α＝90°、β＝98.937°、γ＝90°。
2. a method for preparing a perovskite single crystal material based on imidazole organic cations according to claim 1, wherein: the method comprises the following steps:
imidazole and PbO are added into a halogen acid solution according to the molar ratio of 4:1-16:1, and an anti-solvent method or a program cooling method is adopted to prepare a perovskite single crystal material; wherein the halogen acid is HBr or HCl.
3. The method for preparing the perovskite single crystal material based on imidazole organic cations according to claim 2, which is characterized in that: when the anti-solvent method is adopted for preparation, the anti-solvent is diethyl ether.
4. The method for preparing the perovskite single crystal material based on imidazole organic cations according to claim 2, which is characterized in that: when the preparation is carried out by adopting a program cooling method, the heating temperature is 90-110 ℃, and the heat preservation is carried out for 1.5-2.5 hours.
5. The method for preparing perovskite single crystal material based on imidazole organic cations according to claim 4, wherein the method comprises the following steps: the cooling rate is 1-2 deg.c/hr.
6. A method for preparing a perovskite single crystal material based on imidazole organic cations according to any one of claims 2 to 5, characterized in that: the mol ratio of the imidazole to the PbO is 8:1-12:1.
7. Use of a perovskite single crystal material based on imidazole organic cations according to claim 1, characterized in that: the material is used as a white fluorescent light-emitting material.
8. Use of a perovskite single crystal material based on imidazole organic cations according to claim 7, characterized in that: said (C) 3 H 5 N 2 ) 3 PbBr 5 Is an intrinsic defect state luminescence.
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| CN114195721A (en) * | 2021-12-17 | 2022-03-18 | 北京理工大学 | Imidazole cation one-dimensional edge-shared metal halide material, and preparation method and application thereof |
| CN114195718A (en) * | 2021-12-17 | 2022-03-18 | 北京理工大学 | One-dimensional edge-sharing perovskite fluorescent material and preparation method thereof |
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| CN114195718A (en) * | 2021-12-17 | 2022-03-18 | 北京理工大学 | One-dimensional edge-sharing perovskite fluorescent material and preparation method thereof |
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| Hua-Yang Ru,等.Regulating structural asymmetry via fluorination engineering in hybrid lead bromide perovskites.Chem. Commun.2023,第59卷8111-8114. * |
| Runan Chen,等.Broadband white-light emission from a novel two-dimensional metal halide assembled by Pb–Cl hendecahedrons.J. Mater. Chem. C.2022,第10卷9465–9470. * |
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